KR102180532B1 - Method for preparing polyolefin having an excellent environment stress crack resistancnellent using the same - Google Patents

Abstract

The present invention provides a bimodal polyolefin with remarkably improved mechanical properties such as environmental stress cracking resistance (ESCR) with excellent processability in a single CSTR reactor in the process for the development of metallocene HDPE products for injection and bottle caps. Provides a method of manufacturing.

Description

Manufacturing method of polyolefin with excellent environmental stress cracking resistance {METHOD FOR PREPARING POLYOLEFIN HAVING AN EXCELLENT ENVIRONMENT STRESS CRACK RESISTANCNELLENT USING THE SAME}

The present invention relates to a method of producing a polyolefin having excellent processability and excellent mechanical properties by implementing bimodal properties using a specific hybrid supported metallocene catalyst.

The olefin polymerization catalyst system can be classified into a Ziegler Natta and a metallocene catalyst system, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler Natta catalysts have been widely applied to conventional commercial processes since their invention in the 1950s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers. There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a homogeneous complex catalyst and is a single site catalyst. A polymer having a narrow molecular weight distribution and a uniform composition distribution of a comonomer is obtained according to the single active point characteristics, and the stereoregularity of the polymer, copolymerization characteristics, molecular weight, and the like depending on the modification of the ligand structure of the catalyst and the change of polymerization conditions, It has properties that can change crystallinity and the like.

US Patent No. 5,032,562 describes a method of preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. This is a method of producing a bimodal distribution polymer by supporting a titanium (Ti)-based Ziegler-Natta catalyst producing high molecular weight and a zirconium (Zr)-based metallocene catalyst producing low molecular weight on one support. As a result, the supporting process is complicated, and the morphology of the polymer is deteriorated due to the cocatalyst.

U.S. Patent No. 5,525,678 discloses a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a nonmetallocene compound on a carrier. This has a disadvantage in that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for the supporting reaction.

U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but it takes a lot of time and the amount of solvent used to prepare the supported catalyst. In addition, there was a hassle of supporting each of the metallocene catalysts used on the carrier.

Korean Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by polymerizing while changing the combination of catalysts in the reactor by supporting a double-nuclear metallocene catalyst and a single-nuclear metallocene catalyst on a carrier together with an activator. have. However, this method has a limitation in realizing the characteristics of each catalyst at the same time, and also has a disadvantage in that the metallocene catalyst portion is released from the carrier component of the completed catalyst, causing fouling in the reactor.

Polyolefin products applicable to various injection molding fields including injection and bottle caps require processability and various mechanical properties. Among them, long-term properties, the kind of comonomer applied to the polymerization process. In general, comonomers used in commercial processes include butene, hexene, octene, etc. The higher the number of carbons, the better the long-term properties, but the price is high. Is advantageous in terms of cost competitiveness, but is relatively weak in terms of quality according to long-term physical properties.To overcome this, a product using a bimodal process capable of producing low-molecular and high-molecular domains simultaneously with two reactors. Development is necessary, because long-term physical properties can be improved by maximizing comonomer content in the polymer domain, but as seen in the case mentioned above, the bimodal process is likely to overload the downstream process and deteriorate product quality. There is a problem.

Therefore, there is a need for research on the development of a technology that can more effectively manufacture a polyolefin capable of realizing the performance of a bimodal product capable of securing not only processability but also mechanical properties such as long-term properties through a process using a single reactor.

An object of the present invention is to provide a method for producing a polyolefin having bimodal properties with remarkably improved mechanical properties such as environmental stress cracking resistance (ESCR) and excellent processability through a single reactor.

According to an embodiment of the present invention, in the presence of a catalyst composition comprising a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2), polymerizing an olefin-based monomer A method for producing a polyolefin containing; is provided.

[Formula 1]

(Cp ¹ R ¹ ) _n (Cp ² R ² ) M ¹ Z ¹ _3-n

In Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ¹ and R ² are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

n is 1 or 0;

[Formula 2]

In Chemical Formula 2,

R ³ , and R ⁴ are the same as or different from each other, and each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C4 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl Group, wherein R ³ , and R ⁴ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring,

R ⁵ and R ⁶ are the same as or different from each other, and alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Or C1-C20 alkoxy substituted C1-C20 alkyl;

X is a hetero atom with an lone pair of electrons;

M ² is a Group 4 transition metal;

Q is the same or different halogens from each other;

n is 2.

For example, the first metallocene compound represented by Formula 1 may be any one of the compounds represented by the following structural formula.

In addition, the second metallocene compound represented by Formula 2 may be any one of the compounds represented by the following structural formula.

The catalyst composition may further include a carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.

In addition, the olefinic monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-decene, 1-undecene, 1- It may include at least one compound selected from the group consisting of dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene, and 3-chloromethylstyrene.

The polymerization step may be performed by slurry polymerization in a hydrocarbon-based solvent.

In the manufacturing method of the polyolefin of the present invention, it can be carried out in a single CSTR reactor (Single Continuous Stirred Tank Reactor).

According to the present invention, a polyolefin having bimodal properties that significantly improves mechanical properties such as environmental stress cracking resistance (ESCR) with excellent processability in a single CSTR reactor in the process by using a specific hybrid supported metallocene catalyst is effectively used. Can be manufactured.

1 is a process diagram schematically showing a method of manufacturing a polyolefin using a multi-stage reactor according to an existing process.
2 is a process chart schematically showing a method of manufacturing a polyolefin using a single CSRT reactor according to an embodiment of the present invention.
3 is a graph showing the molecular weight distribution of a polymer in the polymerization reaction of polyolefins according to Examples 1, 4, and Comparative Example 1 (lime green: Example 1, purple: Example 4, blue: Comparative Example 1) .
4 is a graph showing the molecular weight distribution of a polymer for the polymerization reaction of polyolefins according to Examples 2 to 3, Examples 5 to 6, and Comparative Examples 2 to 3 (blue: Example 2, red: Example 3, Light blue: Example 5, Orange: Example 6, Light green: Comparative Example 2, Purple: Comparative Example 3).

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include" or "have" are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, elements, or combinations thereof is not preliminarily excluded.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in more detail.

According to an embodiment of the present invention, in the presence of a catalyst composition comprising a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2), polymerizing an olefin-based monomer There is provided a method for producing a polyolefin comprising a.

[Formula 1]

(Cp ¹ R ¹ ) _n (Cp ² R ² ) M ¹ Z ¹ _3-n

In Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ¹ and R ² are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

n is 1 or 0;

[Formula 2]

In Chemical Formula 2,

R ³ , and R ⁴ are the same as or different from each other, and each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C4 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl Group, wherein R ³ , and R ⁴ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring,

R ⁵ and R ⁶ are the same as or different from each other, and alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Or C1-C20 alkoxy substituted C1-C20 alkyl;

X is a hetero atom with an lone pair of electrons;

M ² is a Group 4 transition metal;

Q is the same or different halogens from each other;

n is 2.

On the other hand, in general, metallocene compounds have excellent reactivity compared to Ziegler catalysts, but the mileage of the catalyst is low, and thus, it is applied as a cascade mode polymerization method. However, in the case of the multistage mode polymerization method, it is not easy to control the operating conditions for each reactor, and the production of bimodal polyolefins having uniform physical properties (or satisfying both processability and mechanical properties) due to unbalanced supply of monomer compounds. Is subject to restrictions. In addition, catalysts known to be capable of synthesizing high molecular weight polyolefins have relatively low activity and thus have a problem in that overall productivity is lowered.

However, as a result of continuous research by the present inventors, in a multistage mode polymerization method using a mixed supported metallocene catalyst, a multistage mode through a method of additionally adding a mixed supported metallocene catalyst and a molecular weight modifier to the reactor after the first step. It has been confirmed that the control of the polymerization method can be facilitated, and more smooth multistage mode operation is possible. In particular, if necessary, when the types of the first mixed supported metallocene catalyst and the additionally added hybrid supported metallocene catalyst are different (e.g., the supported amount of the metallocene compound, the supported metallocene compound If the mixing ratio of these is different), the physical properties of the resulting polymer can be more easily controlled. In addition, through this method, a polyolefin having a large molecular weight and a wide multimodal molecular weight distribution can be produced more effectively. And the polyolefin produced according to this method has excellent mechanical properties and processability, and can be particularly suitably applied for blow molding.

That is, the method for producing a polyolefin according to an embodiment of the present invention includes the first step and the second step as a polymerization process, and in particular, the second step includes the first hybrid supported metal used in the first step. Apart from the sen catalyst, a second hybrid supported metallocene compound, a molecular weight modifier and a molecular weight modifier are additionally added. This method of producing polyolefin enables the production of polyolefins having a large molecular weight as well as polyolefins having a wide multimodal molecular weight distribution. Further, by different types of the first hybrid supported metallocene catalyst and the second hybrid supported metallocene catalyst, the physical properties of the resulting polyolefin can be easily controlled, and ultimately, a polyolefin having a balanced mechanical properties and processability. It is possible to provide.

According to one embodiment of the invention, the first hybrid supported metallocene catalyst and the second hybrid supported metallocene catalyst may be the same or different catalysts. For example, when the types of the first and second hybrid supported metallocene catalysts are the same, the problem of lowering productivity due to low mileage of the metallocene compound can be solved, and polyolefin having a larger molecular weight if necessary Can be manufactured. And, when the types of the first and second hybrid supported metallocene catalysts are different, as described above, the physical properties of the produced polyolefin can be easily controlled, and a polyolefin having a wider multimodal molecular weight distribution can be prepared. .

Meanwhile, the metallocene catalyst composition of the present invention may include at least one first metallocene compound represented by Chemical Formula 1, and at least one second metallocene compound represented by Chemical Formula 2.

The metallocene compounds of Formulas 1 and 2 will be described in more detail as follows. The metallocene catalyst composition of the present invention is characterized in that two or more different metallocene compounds are hybridized and used together.

The first metallocene compound represented by Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

In addition, the second metallocene compound represented by Formula 2 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

In addition, in Chemical Formulas 1 and 2, the Group 4 transition metal may include titanium, zirconium, and hafnium, but is not limited thereto.

[Formula 1]

(Cp ¹ R ¹ ) _n (Cp ² R ² ) M ¹ Z ¹ _3-n

In Formula 1, R ¹ and R ² may be preferably hydrogen, i -propyl, n -butyl, t -butyl, t -butoxyhexyl, n -hexyl, butene, phenyl, or benzyl, and Z ¹ may preferably be chlorine or methyl. In addition, in Formula 2, R ³ and R ⁴ are preferably hydrogen, n -butyl, t -butoxyhexyl, methyl, cyclohexylmethylene, trimethylsilyl (TMS) methylene, phenyl, or benzyl, R ⁵ and R ⁶ may preferably be methyl, t -butoxyhexyl, or phenyl, X may preferably be N, S, or O, and Q is preferably chlorine or methyl. I can.

The metallocene catalyst composition of the present invention may further include a carrier and a cocatalyst compound.

The carrier is not limited in its configuration as long as it is a type of metal, metal salt, or metal oxide that is usually used in a supported catalyst. Specifically, it may be in a form including any one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia. In particular, as the carrier, a carrier containing a hydroxy group on the surface may be used, and preferably, a carrier having a highly reactive hydroxyl group and a siloxane group may be used after drying to remove moisture from the surface. For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

The drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. When the drying temperature of the carrier is less than 200°C, there is too much moisture to react with the surface moisture and the cocatalyst, and when it exceeds 800°C, the pores on the surface of the carrier are combined and the surface area decreases, and there are many hydroxyl groups on the surface. It is not preferable because it disappears and only siloxane groups remain, and the reaction site with the cocatalyst decreases.

The amount of hydroxy group on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 1 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol/g, the reaction site with the cocatalyst is small, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. not.

In addition, the cocatalyst compound may be one or more of the compounds represented by the following Chemical Formula 3, Chemical Formula 4, or Chemical Formula 5.

[Formula 3]

-[Al(R ⁷ )-O] _n-

In Chemical Formula 3,

R ⁷ may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a halogen-substituted C 1 to C 20 hydrocarbon;

n is an integer of 2 or more;

[Formula 4]

J(R ⁸ ) ₃

In Chemical Formula 4,

R ⁸ may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a halogen-substituted C 1 to C 20 hydrocarbon;

J is aluminum or boron;

[Formula 5]

^{[EH] + [Z 2 A} '4] - or ^{[E] + [Z 2 A} ' 4] -

In Chemical Formula 5,

E is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z ² is a group 13 element;

A'may be the same as or different from each other, and each independently one or more hydrogen atoms is substituted or unsubstituted with halogen, C 1 to C 20 hydrocarbon, alkoxy or phenoxy, a C 6 to C 20 aryl group or C 1 to C 20 alkyl group to be.

Examples of the compound represented by Chemical Formula 3 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and a more preferable compound is methylaluminoxane.

Examples of the compound represented by Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc. are included, and more preferable compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Formula 5 include triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetra Pentafluorophenyl boron, N,N-dimethylanilinium-tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl ) Aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra ( p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-dimethylanilinium tetraphenylaluminum, N,N-diethylanilinium-tetrapentafluorophenylaluminum, di Ethyl ammonium tetrapenta tetraphenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o,p-dimethylphenyl) boron , Tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium-tetrapentafluorophenyl boron, and the like.

Preferably, alumoxane may be used, more preferably methyl alumoxane (MAO), which is an alkyl alumoxane.

When the metallocene compounds of Formulas 1 and 2 and the cocatalyst compounds of Formulas 3 to 5 are used in the catalyst composition of the present invention in a form supported on a carrier, the metallocene compound is about 0.5 To about 20 parts by weight, the cocatalyst compound of Formulas 3 to 5 may be included in an amount of about 1 to about 1,000 parts by weight. Preferably, with respect to 100 parts by weight of the carrier, about 1 to about 15 parts by weight of the metallocene compound, and about 10 to about 500 parts by weight of the cocatalyst compound of Formulas 3 to 5 may be included, and most preferably the With respect to 100 parts by weight of the carrier, about 1 to about 100 parts by weight of the metallocene compound, and about 40 to about 150 parts by weight of the cocatalyst may be included.

In addition, the mass ratio of the total transition metal to the carrier contained in the metallocene compounds of Formulas 1 and 2 may be 1: 10 to 1: 1,000. When the carrier and the metallocene compound are included in the mass ratio, the optimum shape may be exhibited. In addition, the mass ratio of the cocatalyst compound of Formulas 3 to 5 to the carrier may be 1:1 to 1:100. When the cocatalyst compound of Formulas 3 to 5 and the metallocene compound are included in the mass ratio, the activity and the microstructure of the polymer can be optimized.

In preparing a hybrid supported metallocene catalyst using the above-described first and second metallocene compounds and a cocatalyst, etc., after supporting the first metallocene compound and the cocatalyst on a support, the second A metallocene compound and a cocatalyst may be supported, but the present invention is not limited thereto. A washing step using a solvent may be additionally performed between each of these supporting steps.

In the method for producing a polyolefin of the present invention, the step of polymerizing the olefin-based monomer includes at least one first metallocene compound represented by Formula 1 and at least one agent selected from the compound represented by Formula 2. 2 It can be carried out in the presence of a catalyst composition comprising a metallocene compound.

In the polymerization step, a polyolefin may be prepared by polymerizing any olefin-based monomer. Specific examples of the olefinic monomers that can be used at this time include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-decene, 1-undee Sen, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene, or 3-chloromethylstyrene. In one example of such a manufacturing method, polyethylene is prepared using ethylene, or with ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-heptene , 1-decene, 1-undecene, or 1-dodecene may be copolymerized with an alpha olefin to prepare an ethylene-alpha olefin copolymer.

In particular, the present invention uses a catalyst composition comprising a first metallocene compound and a second metalocene compound, and the physical properties of the polyolefin produced even by using a single reactor can be easily controlled, and a wider multimodal molecular weight distribution A polyolefin having may be prepared.

In addition, according to another embodiment, ethylene and a comonomer may be used together as the olefinic monomer; The comonomer is propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, norbornene , Ethylidene norbornene, styrene, alpha-methylstyrene, and may be one or more compounds selected from the group consisting of 3-chloromethylstyrene.

At this time, the comonomer may be used in an amount of about 30% by weight or less, or 0 to about 20% by weight, or about 0.1 to 15% by weight based on the content of ethylene, and may be copolymerized. When the comonomer of such an amount is copolymerized, the finally produced polyolefin can exhibit excellent mechanical properties and processability within a density range suitable for blow molding. However, when an excessively large amount of comonomer is used, the density of the polymer may be lowered, resulting in a decrease in flexural strength.

Meanwhile, the catalyst composition may further include a molecular weight modifier. The molecular weight modifier itself does not exhibit activity as an olefin polymerization catalyst, but may be a compound capable of forming a polyolefin having a larger molecular weight and a broader molecular weight distribution by assisting the activity of the metallocene catalyst. Due to the action of such a molecular weight modifier, polymerization of the olefin-based monomer can be effectively carried out.

According to one embodiment, the molecular weight modifier may include a mixture of a cyclopentadienyl metal compound represented by Formula 6 below and an organic aluminum compound represented by Formula 7 below, or a reaction product thereof.

[Formula 6]

^{Cp 3 Cp 4 M 3 X '} 2

In Formula 6,

Cp ³ and Cp ⁴ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, or a ligand containing a substituted or unsubstituted fluorenyl group, and M ^{3 is a} group 4 transition metal element. , X'is halogen;

[Formula 7]

R ⁹ R ¹⁰ R ¹¹ Al

In Chemical Formula 7,

R ⁹ , R ¹⁰ , and R ¹¹ are each independently an alkyl group or halogen having 4 to 20 carbon atoms, and R ⁹ , R ¹⁰ , and At least one of R ¹¹ is an alkyl group having 4 to 20 carbon atoms.

The molecular weight modifier itself does not exhibit activity as an olefin polymerization catalyst, and its mechanism of action is not specifically identified, but the preparation of a polyolefin having a larger molecular weight and a broader molecular weight distribution by assisting the activity of the metallocene catalyst Makes it possible.

Due to the action of such a molecular weight modifier, for example, in the case of producing a polyolefin in a multistage reactor to be described later, even if a large number of metallocene catalysts are consumed in the reactor at the front, the polyolefin having a higher molecular weight may be polymerized in the reactor at the rear stage. Polyolefins having a large molecular weight and a broad multimodal molecular weight distribution can be prepared.

According to one embodiment, the molecular weight modifier may be used in a mixture state in which the compounds of Formula 6 and Formula 7 do not react with each other. In addition, the molecular weight modifier is a reaction product of the compounds of Formulas 6 and 7, for example, in which the metal elements of these compounds are bonded to each other via one of X'and/or R _d , R _e and R _f It can be used in the form of an organometallic complex. In this case, together with the organometallic complex, some unreacted compounds of Formula 6 and/or Formula 7 may be further included.

Meanwhile, in the molecular weight modifier, specific examples of the cyclopentadienyl metal compound of Formula 6 include biscyclopentadienyl titanium dichloride, biscyclopentadienyl zirconium dichloride, biscyclopentadienylhafnium dichloride, and bis. Neil titanium dichloride, bisfluorenyl titanium dichloride, etc. are mentioned. In addition, specific examples of the organic aluminum compound of Formula 7 include triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diisobutyl aluminum chloride, dihexyl aluminum chloride, or isobutyl aluminum dichloride.

And, the compound of Formula 6 and the compound of Formula 7 are about 1:0.1 to 1:100, based on the molar ratio of the metal element (M) contained in Chemical Formula 6 and aluminum (Al) contained in Chemical Formula 8, Alternatively, it is preferably used in a molar ratio of about 1:0.5 to 1:10.

In addition, the molecular weight modifier may be used in an amount of about 10 ^-7 to 10 ^-1 parts by weight, or about 10 ^-5 to 10 ^-2 parts by weight based on 100 parts by weight of the olefinic monomer. As used in this content range, the action and effect due to the addition of the molecular weight control agent are optimized, and a polyolefin having excellent physical properties can be obtained.

Meanwhile, according to an exemplary embodiment of the present invention, the polymerization step may be performed in a slurry phase polymerization in a hydrocarbon-based solvent (eg, an aliphatic hydrocarbon-based solvent such as hexane, butane, and pentane). As already described above, as the first and second metallocene compounds and the molecular weight modifier exhibit excellent solubility in aliphatic hydrocarbon-based solvents, they are stably dissolved and supplied to the reaction system, so that the polymerization reaction in each step It can be done effectively.

And, the method of manufacturing a polyolefin according to an embodiment of the present invention may be performed in a single CSTR reactor (Single Continuous Stirred Tank Reactor). A schematic process using such a single CSTR reactor is as shown in FIG. 2.

In this single CSTR reactor, in the presence of a metallocene catalyst composition (Cat.), a step of polymerizing an olefinic monomer (C2) is performed. Polymerization by additionally adding a molecular weight modifier, etc. together with the catalyst composition and olefinic monomer including the first metallocene compound and the second metallocene compound as described above in the single CSTR reactor (Single Continuous Stirred Tank Reactor). The steps are carried out. In the single CSTR reactor, polymerization may proceed in the presence of an inert gas such as nitrogen, for example. The inert gas may play a role of prolonging the reaction activity of the metallocene compound by suppressing the rapid reaction of the metallocene compound at the beginning of the polymerization reaction, and the amount of inert gas used in the reactor may be adjusted in consideration of the reaction activity. I can.

In the polymerization reactor, hydrogen gas may be used for the purpose of controlling the molecular weight and molecular weight distribution of the polyolefin.

And, in the polymerization step, in order to remove moisture, oxygen, etc. in the reactor that may inhibit the activity of the catalyst compound, an organic aluminum compound may be further added. As a non-limiting example, the organic aluminum compound may be one or more compounds selected from the group consisting of trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride, and alkyl aluminum sesqui halide. More specifically, the organic aluminum compound is Al(C ₂ H ₅ ) ₃ , Al(C ₂ H ₅ ) ₂ H, Al(C ₃ H ₇ ) ₃ , Al(C ₃ H ₇ ) ₂ H, Al(iC ₄ H ₉ ) ₂ H, Al(C ₈ H ₁₇ ) ₃ , Al(C ₁₂ H ₂₅ ) ₃ , Al(C ₂ H ₅ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ ) ₂ H, Al (iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl, or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ or the like. These organoaluminum compounds may be continuously introduced into each reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of reaction medium introduced into each reactor for proper moisture removal.

Meanwhile, in the reactor, the residence time of the raw material may be applied without particular limitation as long as it is a range capable of forming a polyolefin having an appropriate molecular weight distribution and density distribution. However, according to one embodiment, the residence time in the reactor may be adjusted to about 1 to 5 hours. That is, if the residence time is shorter than 1 hour, the low molecular weight polyolefin is not properly formed and the molecular weight distribution is narrowed, so that the physical properties of the final polyolefin may be deteriorated. Conversely, if the residence time is too long, it is not preferable in terms of productivity.

And, the polymerization reaction temperature may be about 70 to 100 ℃. If the polymerization reaction temperature is too low, it is not appropriate in terms of polymerization rate and productivity, and conversely, if the polymerization reaction temperature is higher than necessary, fouling in the reactor may be caused.

In addition, the polymerization reaction pressure may be about 5 to 10 bar in order to maintain a stable continuous process state.

In addition, an organic solvent may be further used as a reaction medium or diluent in the polymerization reaction. Such an organic solvent may be used in an amount sufficient to properly perform slurry polymerization or the like in consideration of the content of the olefinic monomer.

The polyolefin formed by the polymerization reaction may be a low molecular weight polyolefin having a weight average molecular weight of about 50,000 to 300,000 g/mol, and may have a molecular weight distribution of about 5 to 100.

In addition to the above-described steps, the method for producing the polyolefin may further include steps commonly employed in the technical field to which the present invention pertains.

Meanwhile, a polyolefin having a large molecular weight and a wide multimodal molecular weight distribution may be finally prepared through a series of polymerization reactions.

That is, according to another embodiment of the present invention, a polyolefin prepared according to the method described above and having a multimodal molecular weight distribution is provided.

These polyolefins may have a large weight average molecular weight of about 100,000 to 500,000 g/mol by the action of the first and second metallocene compounds and molecular weight modifiers in the polymerization reactions of the first and second steps described above, It may have a broader bimodal or multimodal molecular weight distribution.

Due to such a large molecular weight and a wide multimodal molecular weight distribution, the polyolefin prepared according to the method of one embodiment may exhibit excellent mechanical properties and processability at the same time. Therefore, the polyolefin has a melt flow rate ratio (MFRR) suitable for processing, and moldability, impact strength, tensile strength, environmental stress cracking resistance (ESCR), and stress cracking resistance (Full Notch Creep Test) , FNCT), etc. are excellent. In addition, the polyolefin has excellent die swell properties and can simultaneously satisfy excellent mechanical properties and processability, and thus can be particularly suitably applied as a polymer for blow molding.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the content of the present invention is not limited thereby.

< Example >

< Metallocene Compound preparation Example >

Synthesis Example 1: Synthesis of catalyst precursor [ ^t Bu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂

Using 6-chlorohexanol, t-Butyl-O-(CH ₂ ) ₆ -Cl was prepared by the method suggested in the literature (Tetrahedron Lett. 2951 (1988)), and NaCp was reacted thereto. t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80°C / 0.1 mmHg).

In addition, t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 °C, and normal butyl lithium (n-BuLi) was slowly added, the temperature was raised to room temperature, and then reacted for 8 hours. Made it. The above-described lithium salt solution was slowly added to the suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 mL) at -78 °C again, and room temperature It was further reacted for 6 hours. All volatile substances were vacuum-dried, and hexane solvent was added to the obtained oily liquid substance to filter it out. After vacuum drying the filtered solution, hexane was added to induce a precipitate at low temperature (-20°C).

The obtained precipitate was filtered at low temperature to obtain a white solid [ ^t Bu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound (yield 92%).

¹ H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7 to 1.3 (m, 8H), 1.17 (s, 9H)

Synthesis example 2: catalyst precursor [ t -Bu-O-(CH ₂ ) ₆ (CH ₃ )]Si ( CpPy )( t - Bu -N) TiCl ₂ of synthesis

After dissolving 13.8 g (80 mmol) of mCPBA (m-Chloroperoxylbenzoic acid, Aldrich) in 100 mL of dichloromethane (DCM), 5.7 mL (50 mmol) of 2,3-cyclopentenopyridine was slowly added dropwise. After removing the solvent, 1.1 g (8 mmol) of the obtained N-oxide was added to an excess of acetic anhydride (Ac ₂ O) and stirred at 100° C. for 2 hours. Residual ethyl acetate (Ac ₂ O) was removed through vacuum drying, and an acetate compound in the form of yellow oil was obtained through a column. The obtained acetate was added to 5.5 mL of sulfuric acid and reacted at 130° C. for 1 hour. After that, the mixture was stirred overnight at room temperature to obtain 2.3 g of 5H-cyclopenta[β]pyridine (CpPy) (yield 40%).

¹ H NMR (300 MHz, CDCl ₃ ): 8.45 (1H, d), 7.69 (1H, d), 7.04 (2H, m), 6.85 (1H, d), 3.39 (2H, s)

1.4 g (12 mmol) of 5H-cyclopenta[β]pyridine (CpPy) prepared in this way and 24 mL of THF were added to the reactor, and the reactor temperature was cooled to -20 °C. After 4.8 mL of n-BuLi was added to the reactor, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature. Thereafter, the reactor temperature was cooled to -20 °C, and 3.26 g (3.5 mL) of methyl(6-t-butoxyhexyl)-dichlorosilane in the same amount was added to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reactor temperature was cooled to 0° C., and 2 equivalents of t-BuNH ₂ were added. The reactor was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, THF was removed and 40 mL of hexane was added to obtain a filter solution to remove the resulting salt. After the filter solution was added to the reactor again, hexane was removed at 70° C. to obtain a yellow solution. The obtained yellow solution was confirmed to be a methyl(6-t-butoxy-hexyl)(CpPy)t-butylaminosilane compound through 1H-NMR.

TiCl ₃ (THF) ₃ (12 mmol) was rapidly added to the dilithium salt of the ligand at -78 ℃ synthesized in THF solution from n-BuLi and the ligand methyl(6-t-butoxy-hexyl)(CpPy)t-butylaminosilane. I did. The reaction solution was stirred for 12 hours while slowly raising from -78 °C to room temperature. After stirring for 12 hours, an equivalent of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution having a blue color was obtained. After removing THF from the resulting reaction solution, hexane was added to filter the product. After removing hexane from the filter solution to be obtained, it was confirmed from ¹ H-NMR to be the desired [ t -Bu-O-(CH ₂ ) ₆ (CH ₃ )]Si(CpPy)( t- Bu-N)TiCl ₂ compound.

¹ H NMR (500 MHz, CDCl ₃ ): 8.56 (1H, d), 7.71 (1H, d), 7.22 (2H, m), 6.97 (1H, d), 3.51 (2H, m), 1.45 ~ 0.31 ( 10H, m), 1.29 (18H, m), 0.28 ~ 0.12 (3H, m)

Synthesis example 3: catalyst precursor (CH ₃ ) ₂ Si[( t -Bu-O-(CH ₂ ) ₆ )(CpPy)]( t -Bu-N)TiCl ₂ of synthesis

T-butoxyhexylchloride equivalent to 5H-cyclopenta[β]pyridine (CpPy) was reacted in 30 mL of THF to obtain the desired t -Bu-O-(CH ₂ ) ₆ (CpPy). 12 mmole of t -Bu-O-(CH ₂ ) ₆ (CpPy) and 24 mL of THF were added to the reactor, and the reactor temperature was cooled to -20 °C. After 4.8 mL of n-BuLi was added to the reactor, the reactor was stirred for 12 hours while slowly raising the temperature to room temperature. Thereafter, the reactor temperature was cooled to -20 °C, and 1.55 g (1.4 mL) of dimethyldichlorosilane in the same amount was added to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reactor temperature was cooled to 0° C., and 2 equivalents of t-BuNH ₂ were added. The reactor was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, THF was removed and 40 mL of hexane was added to obtain a filter solution to remove the resulting salt. After the filter solution was added to the reactor again, hexane was removed at 70° C. to obtain a yellow solution. The obtained yellow solution was confirmed to be a dimethyl(6-t-butoxy-hexyl)(CpPy)t-butylaminosilane compound through 1H-NMR.

TiCl ₃ (THF) ₃ (12 mmol) was rapidly added to the dilithium salt of the ligand at -78 ℃ synthesized in THF solution from n-BuLi and the ligand dimethyl(6-t-butoxy-hexyl)(CpPy)t-butylaminosilane. I did. The reaction solution was stirred for 12 hours while slowly raising from -78 °C to room temperature. After stirring for 12 hours, an equivalent of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution having a blue color was obtained. After removing THF from the resulting reaction solution, hexane was added to filter the product. After removing hexane from the filter solution to be obtained, the desired (CH ₃ ) ₂ Si[( t -Bu-O-(CH ₂ ) ₆ )(CpPy)]( t -Bu-N)TiCl ₂ compound was obtained from ¹ H-NMR. Confirmed.

¹ H NMR (500 MHz, CDCl ₃ ): 8.44 (1H, d), 7.61 (1H, d), 7.04 (1H, m), 6.76 (1H, d), 3.48 (2H, m), 1.61 ~ 0.28 ( 10H, m), 1.17 (12H, s), 0.91 (3H, s)

< Metallocene Of supported catalyst preparation Example >

Supported catalyst Manufacturing example One

First, silica (SYLOPOL 948 manufactured by Grace Davison) was dehydrated under vacuum at 400° C. for 12 hours.

100 mL of a toluene solution was added to a glass reactor at room temperature, 10 g of prepared silica was added, and the mixture was stirred while raising the reactor temperature to 40°C. After sufficiently dispersing the silica, 60.6 mL of a 10 wt% methylaluminoxane (MAO)/toluene solution was added and the temperature was raised to 80° C., followed by stirring at 200 rpm for 16 hours.

Thereafter, the temperature was lowered to 40° C. and washed with a sufficient amount of toluene to remove unreacted aluminum compounds. 100 mL of toluene was added again, and the catalyst precursor prepared in Synthesis Example 1 (Chemical Formula 1) was added and stirred for 1 hour, and then the catalyst precursor prepared in Synthesis Example 2 (Chemical Formula 2) was added to 2 Stir for hours. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and the toluene was removed under reduced pressure at 40° C. to prepare an olefin-carrying catalyst.

Supported catalyst Manufacturing example 2

A metallocene-supported catalyst was prepared in the same manner as in Preparation Example 1 of the supported catalyst, except that the catalyst precursor prepared in Synthesis Example 3 was used instead of the catalyst precursor prepared in Synthesis Example 2 in Preparation Example 1.

<of polyethylene polymerization Example >

Example 1: Preparation of polyolefin

First, a single CSTR reaction apparatus including a reactor having a capacity of 0.2 m ³ as shown in FIG. 2 was prepared.

Into a 2L stainless autoclave reactor equipped with a jacket that can supply external cooling water for polymerization temperature control, isobutane and ethylene are flowed once and five times at about 110°C, respectively, to remove impurities. , The temperature was lowered to 80°C. 900 mL of isobutane and 0.02 mmol of triethylaluminum (TEAL) as an impurity removing agent were added to the washed reactor, stirred at 80° C., and then 100 mL of hexane and about 60 mg of the supported catalyst prepared in Preparation Example 1 were added. And, while ethylene is added so that the partial pressure of ethylene is 160 psig, 1-butene (weight%, the amount of 1-butene added to the input ethylene) is added in an amount of 0.05% by weight, and hydrogen (mg/kgC ₂ , input ethylene) An input amount (mg) of hydrogen per 1 kg was added in an amount of 300 mg/kgC ₂ to maintain the total pressure of the reactor at 80° C. and polymerization was performed for 60 minutes, while the partial pressure of ethylene was kept constant during polymerization. And hydrogen was continuously added in conjunction with ethylene.

Example 2-3: Preparation of polyolefin

Polyethylene was prepared in the same manner as in Example 1, except that the mixed supported metallocene catalyst according to Preparation Example 1 was used and the 1-butene and hydrogen contents were different.

Example 4: Preparation of polyolefin

Polyethylene was prepared in the same manner as in Example 1, except that the hybrid supported metallocene catalyst according to Preparation Example 2 was used instead of the hybrid supported metallocene catalyst according to Preparation Example 1.

Example 5-6: Preparation of polyolefin

Polyethylene was prepared in the same manner as in Example 4, except that the mixed supported metallocene catalyst according to Preparation Example 2 was used instead of the hybrid supported metallocene catalyst according to Preparation Example 1, and the 1-butene and hydrogen contents were different. Was prepared.

Comparative example 1~3

In Comparative Example 1, a polyethylene product (XP6070) manufactured by a unimodal process as shown in FIG. 2 was prepared using a metallocene catalyst, and in Comparative Examples 2 and 3, a Ziegler-Natta catalyst was used. A polyethylene product (Comparative Example 2: ME1000, Comparative Example 3: CAP602) manufactured by a bimodal process as shown in 1 was prepared.

Test example

The properties of the polyethylene prepared in the Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

1) Molecular weight distribution (PDI, Mw/Mn): The weight average molecular weight was measured by dividing the number average molecular weight by using Gel Permeation Chromatography (GPC).

2) Melt Index (MI): It was measured according to ASTM D1238 under a temperature of 190°C and a load of 21.6 kg.

3) Spiral Flow Length:

A spiral flow test was performed according to ASTM D 3123 to measure a spiral flow length (cm).

4) Environmental stress cracking resistance (ESCR):

Environmental stress cracking resistance (ESCR, hr) was measured by the method of ASTM D 1693.

catalyst fair MI
(2.16, g/10min) density
(g/cm ³ ) Weight average molecular weight
(Mw) Molecular weight distribution
(Mw/Mn) Spiral Flow (cm) ESCR (hr) Comparative Example 1 Metallocene Unimodal 9.5 0.960 58,000 3.5 17 3 Comparative Example 2 Ziegler-Natta Bimodal 0.9 0.952 153,000 10.2 13 50 Comparative Example 3 Ziegler-Natta Bimodal 0.8 0.952 136,000 9.8 10 160 Example 1 Supported Catalyst Preparation Example 1 Metallocene/unimodal 7.8 0.960 90,000 5.7 19 4 Example 2 Supported Catalyst Preparation Example 1 Metallocene/unimodal 0.3 0.950 180,000 11.8 19 300 Example 3 Supported Catalyst Preparation Example 1 Metallocene/unimodal 0.2 0.951 200,000 10.6 15 300 Example 4 Supported Catalyst Preparation Example 2 Metallocene/unimodal 8.3 0.960 82,000 5.9 20 4 Example 5 Supported Catalyst Preparation Example 2 Metallocene/unimodal 0.4 0.952 175,000 12.5 20 270 Example 6 Supported Catalyst Preparation Example 2 Metallocene/unimodal 0.5 0.952 192,000 14.1 18 230

As shown in Table 1, in the case of Examples 1 to 6 in which olefin polymerization was performed in a single CSTR reactor using a specific hybrid supported metallocene catalyst according to the present invention, a melt index equal to or higher than Comparative Examples 1 to 3 It has a molecular weight distribution and has high environmental stress cracking resistance. In the case of Examples 1 to 3 and Examples 4 to 5, as a result of comparing properties due to structural differences of the catalyst precursors under similar polymerization conditions, respectively, overall similarly excellent properties were exhibited. However, it was confirmed that the molecular weight and molecular weight distribution slightly differ depending on the position of the alkoxy alkyl substituent. That is, it can be seen that the molecular weight and molecular weight distribution tend to increase in the case where the alkoxy alkyl substituent is in the indenyl (Cp) unit than in the case where the alkoxy alkyl substituent is in the Si bridge (Preparation Example 1).

1st Reactor: 1st reactor
2nd Reactor: 2nd Reactor
Cat.: Hybrid supported metallocene catalyst
C2: ethylene monomer

Claims (7)

Polymerizing an olefin-based monomer in the presence of a catalyst composition comprising a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula (2)
Method for producing a polyolefin comprising:
[Formula 1]
(Cp ¹ R ¹ ) _n (Cp ² R ² ) M ¹ Z ¹ _3-n
In Formula 1,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ¹ and R ² are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
n is 1 or 0;
[Formula 2]

In Chemical Formula 2,
R ³ and R ⁴ are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group, C1 to C20 Alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C4 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group And, the R ³ and R ⁴ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring,
R ⁵ and R ⁶ are the same as or different from each other, and alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Or C1-C20 alkoxy substituted C1-C20 alkyl;
X is a hetero atom with an lone pair of electrons;
M ² is a Group 4 transition metal;
Q is the same or different halogens from each other;
n is 2.
The method of claim 1,
The first metallocene compound represented by Formula 1 is a method of producing a polyolefin, which is any one of compounds represented by the following structural formula.

The method of claim 1,
The second metallocene compound represented by Formula 2 is a method of producing a polyolefin, which is any one of the compounds represented by the following structural formula.

The method of claim 1,
The catalyst composition is a method for producing a polyolefin further comprising a carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.
The method of claim 1,
The olefin monomers are ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-decene, 1-undecene, 1-dodecene , Norbornene, ethylidene norbornene, styrene, alpha-methylstyrene, and a method for producing a polyolefin comprising at least one compound selected from the group consisting of 3-chloromethylstyrene.
The method of claim 1,
The polymerization step is a method for producing a polyolefin in which the polymerization is performed in a slurry phase in a hydrocarbon-based solvent.
The method of claim 1,
A method for producing polyolefins carried out in a single CSTR reactor (Single Continuous Stirred Tank Reactor).

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